The epoxy intermediates and resins industry (Encyclopedia of Chemical Technology, Volume 9. Fourth Edition. John Wiley and Sons Page 730) is a multibillion dollar business that is based on the following technology that involves no less than ten chemical reactions. This application is a continuation-in-part of Ser. No. 60/284,325 filed Apr. 17, 2001.
Benzene+propylenexe2x86x92isopropylbenzene
Isopropylbenzenexe2x86x92cumene hydroperoxide
Cumene hydroperoxidexe2x86x92phenol+acetone.
Phenol+acetonexe2x86x92xe2x80x9cBis-Axe2x80x9d or Phenol+formaldehydexe2x86x92xe2x80x9cBis-Fxe2x80x9d
Propylene+chlorinexe2x86x92allyl chloride
Allyl chloride+sodium hydroxide+chlorinexe2x86x92propylene chlorohydrins
Propylene chlorohydrins+sodium hydroxidexe2x86x92epichlorohydrin
Bis-A+epichlorohydrin+NaOHxe2x86x92xe2x80x9cBis-A glycidol etherxe2x80x9d
Bis-A glycidol ether+Bis-Axe2x86x92epoxy resin
Sodium chloride+waterxe2x86x92chlorine+sodium hydroxide.
Several aspects of the above reaction sequence have negative process implications with regards to yields, chlorinated byproducts, hydraulic load and biological hazards. These include but are not limited to the following: (a) benzene is a known carcinogen, (b) Bis-A is an endocrine disrupter (mimics estrogen), (c) chlorination of propylene to allyl chloride (step 5) and the addition of hypochlorous acid (step 6) yield higher chlorinated byproducts resulting in xcx9c⅓ pounds of chlorinated waste per pound of epichlorohydrin. In addition, the process requires a chlor-alkali facility, hence a local source of salt and huge volumes of water. The products and processes of the present invention ameliorate if not eliminate some of the disadvantages of prior art epoxy products and processes.
The present invention relates to the preparation of bis-esters and ethers of allylarylphenols and the epoxidation of the allyl moiety to provide novel bis-epoxide ester and ether intermediates useful in the preparation of epoxy resins. The epoxy ethers and esters of carboxylic, carbonic, phosphoric and sulfonic acids of the present invention are represented by the following formulas: 
where Y is a CO, CO2 or SO2, AR is a divalent unsubstituted or substituted aromatic, halogen-substituted aromatic or cyano-substituted aromatic hydrocarbon radical having from 6 to 20 carbon atoms, Z is a divalent hydrocarbon or ether radical having from 1 to 20 carbon atoms, including YZY being CO, and R* is an alkyl, aryl, arylalkyl, alkoxy, aryloxy or arylalkoxy radical having from 0-20 carbon atoms.
Preferred aromatic xe2x80x9cARxe2x80x9d radicals include divalent benzene, naphthalene, toluene, chlorobenzene, cyanobenzene, xylene and ethylbenzene radicals. Preferred hydrocarbon xe2x80x9cZxe2x80x9d radicals include divalent aliphatic radicals such as divalent methane, ethane, butane, and cyclohexane, divalent aromatic radicals such as divalent benzene, toluene, xylene and ethylbenzene radicals. Preferred ether xe2x80x9cZxe2x80x9d radicals include such divalent radicals as divalent ethoxyethane, ethoxypropane, propoxypropane, butoxyethane methoxybenzene, and ethoxybenzene. Preferred R* radicals include methyl, ethyl, propyl, isobutyl, cyclohexyl, phenyl, benzyl, naphthyl, toluyl and xylyl.
The preparation of allylarylphenols used in the present invention is well documented in the chemical literature and is illustrated for 2-allylphenol. The formation of the ether and the rearrangement are carried out in the same reactor.
C6H5OH+CH2xe2x95x90CHCH2X+basexe2x86x92C6H5OCH2CHxe2x95x90CH2+HX, 
where X is Cl, Br, acetate, tosylate, or similar leaving group.
C6H5OCH2CHxe2x95x90CH2+H+xe2x86x922-CH2xe2x95x90CHCH2C6H4OH 
The preparation of bis-aromatic disulfonyl chlorides is also well-documented in the literature and is achieved via the sulfonation or chlorosulfonation of aromatic compounds (xe2x80x9cFriedel Crafts and Related Reactionsxe2x80x9d, Volume 3, Part 2, page 1355, Interscience Publishers, 1964, C. M. Suter, xe2x80x9cOrganic Chemistry of Sulfur Compoundsxe2x80x9d, Chapter 3 John Wiley and Sons, 1944, and xe2x80x9cOrganic Functional Group Preparationsxe2x80x9d, S. R. Sandler and W. Karo, Academic Press 1968, page 506). The reactions are preferably carried out in 1,2-dichloroethane as solvent. If higher reaction temperatures are required for the bis sulfonation, the reaction may be performed without a solvent. Reaction of the aromatic disulfonyl chloride with two equivalents of the allylarylphenol in the presence of an acid acceptor gives the desired bis-sulfonate ester which is converted to the desired bis-epoxide in essentially quantitative yield with standard utilized oxidants e.g., peracetic acid, 3-chloroperbenzoic acid, hydrogen peroxide, t-butyl hydroperoxide etc. The latter two reagents require a metal catalyst (xe2x80x9cOxidations in Organic Chemistryxe2x80x9d, M. Hudlicky, ACS Monograph 186, page 60. American Chemical Society).
The allylarylphenyl ester of dicarboxylic acids are conveniently prepared from the reaction of the dicarboxylic acid dichloride with the allylarylphenol in an inert solvent such as toluene, dichloromethane, 1,2-dichloromethane etc. in the presence of a hydrogen acceptor such as pyridine, triethylamine, etc. The use of the hydrogen acceptor can be eliminated by simply refluxing the phenol and acid chloride in a higher boiling solvent to effect displacement of the anhydrous HCl that may be recovered for alternate uses. If a lower dialkyl ester of the dicarboxylic acid is available, ester exchange of the allylarylphenol in the presence of a transesterification catalyst can serve as an alternative route to the bis-aryl ester (xe2x80x9cEncyclopedia of Chemical Technologyxe2x80x9d, Volume 9. Fourth Edition, John Wiley and Sons, page 755, xe2x80x9cSurvey of Synthesisxe2x80x9d, Calvin Buehler and D. E Pearson, Wiley Interscience 1970, page 101 and xe2x80x9cPreparation of Esters using Polyphosphate Esterxe2x80x9d, J. H. Adams, J. G. Paul and J. R. Lewis, Synthesis, 429-30, 1979). The oxidation methods are identical as described above for the sulfate esters.
In the manner described for the preparation of allylphenyl esters from dicarboxylic acid dichlorides, the allylphenyl esters of dicarbonic acids are prepared from the corresponding bis-chloroformates with two equivalents of allylphenol. Similarly a carbonic acid ester, is prepared from two equivalents of allylphenol and phosgene.
The allylaryl esters of the phosphoric and phosphonic acids are readily prepared from the acid dichlorides since phosphorus oxychloride, POCl3, is the basic phosphorus precursor (xe2x80x9cOrganophosphorus Compoundsxe2x80x9d, G. M. Kosolapoff, John Wiley, 1950). Thus, utilization of an inert solvent and an acid acceptor as described above for the carboxylic acids gives high yields of the desired allylaryl esters that are then oxidized to the bis-epoxides as described above.
The allylaryl ethers are prepared by displacement reactions of the desired dichloride with either the allylaryl phenoxide anion or displacement by the 2,3-epoxypropylphenoxide anion. For substrates that require higher temperatures to carry out the displacement such as 4-chlorophenyl sulfone, the preferred anion is the 2,3-epoxypropylphenoxide. With the allylaryl phenoxide, displacement occurs but the 2,3-olefinic bond undergoes thermal isomerization to the 1,2-olefin. With the more reactive olefins, such as 1,4-dichlorobutane and 3,6-dichloropyridazine, olefin isomerization is not a problem. For unreactive aryl halides, reaction conditions for the Ullman reaction ether synthesis is required. Within the scope of the present invention, optimum reaction conditions can be obtained in a routine manner.
The following are examples of allylarylphenols that may be reacted with either derivatives of organic acids or dihalo compounds to form the compounds of this invention: 2-allylphenol, 2-allyl-6-methylphenol, 4-allyl-2,6-dimethylphenol, 2-allyl-4-dodecylphenol, 2-allyl-4-methoxyphenol, 2-allyl-4-phenoxyphenol, 2-allyl-4-cyclohexylphenol, 3-allyl-4-hydroxy ethyl benzoate, 2-allyl-4-chlorophenol, 2-allyl-4-cyanophenol, 2-allyl-4-benzylphenol, 2-allyl-4-chloromethylphenol, 1-allyl-2-naphthol, and 2-allyl-4-phenylphenol.
The following are examples of the disulfonic acid compounds that can be employed to prepare the diepoxides of the present invention: benzene-1,3-disulfonyl chloride, naphalene-2,6-disulfonyl chloride, phenyl ether-1,4-disulfonyl chloride, 4,4*biphenyldisulfonyl chloride, 2,5-dimethylbenzene-1,3-disulfonyl chloride, 4-octylbenzene-1,3-disulfonyl chloride, 4-methoxybenzene-1,3-disulfonyl chloride, 4-chlorobenzene-1,3-disulfonyl chloride, 4-carboethoxy-1,3-disulfonyl chloride 3,5-pyridinedisulfonyl chloride, 3,5-pyridine-N-oxide disulfonyl chloride, and 2,5-thiophenedisulfonyl chloride.
The following are examples of the dicarboxylic acid compounds which can be employed in the preparation of the novel epoxides of the present invention: terephtholyl chloride, iso-phtholyl chloride, succinoyl choride, adipoyl chloride, 1,4-cyclohexane carboxylic acid dichloride, dimethyl terephthalate, diethyl succinate, 4,4*-biphenyl dicarboxylic acid dichloride, malonyl chlorde, oxaloyl chloride and 3,5-pyridine-dicarboxylic acid dichloride.
The following are examples of the starting materials which can be employed in the formation of the novel bis-epoxide ethers of the present invention: 1,2-dichloroethane, 1,4-dichlorobutane, 1,4-dichloro-2-butene, 1,12-dichlorododecane, 1,4-dichlorocyclohexane, 4-chlorophenyl sulfone, 4-(2-chloroethoxyphenyl)sulfone, 4,4*-dichlorobenzophenone, 2,6-difluorobenzonitrile, 2,4-dichloroacetophenone, 2,4-dichlorotoluene, 2,4-dichloro-1-methyl naphthoate, 2,6-dichloropyridine-N oxide and chlorinated polyethylene glycols having the formula ClCH2CH2(OCH2CH2)XCl where x is a number from 1 to 10.
The condensation of the bis-epoxides of this invention with diphenols, e.g., bisphenol-A, bisphenol-F, 4-hydroxyphenyl sulfone, 4,4*-dihydroxybenzophenone, 4,4*-dihydroxybiphenyl and 1,4-(4-hydroxyphenyl)butane, with dicarboxylic acids, e.g., isophthalic acid, succinic acid and cyclohexane dicarboxylic acid, with aminophenols, e.g., 4-aminophenol, 4-amino-4*-hydroxyphenyl ether, and 4-amino-4*-hydroxybiphenyl, with hydroxy carboxylic acids, e.g., 4-hydroxybenzoic acid and 6-hydroxy-6-hydroxy-2-naphthoic acid, with amino acids, e.g., 4-aminobenzoic acid, and 4-aminophenoxybenzoic acid, with diamines, e.g., 4,4*-diaminophenyl ether 1,3-diamonobenzene and 1,3-diamonipropane or with disulfonamides, e.g., 1,3-benzenedisulfonice acid:bis-N-methyl amide results in new and valuable epoxy resins for protective coatings, structural composites, electrical laminates and adhesives. The chemistry provides the opportunity to manufacture resins with fewer chemical transformations, less capital and a reduction in the waste load associated with the Bis-A/epichlorohydrin technology. The resins can be obtained from the bis-epoxides using condensation procedures established in the art. An example of a resin synthesis from readily available starting materials using the epoxide route of the present invention that requires only six chemical transformation is outlined below:
1. toluenexe2x86x92phenol (T. Shikada et al, J. Chem. Soc., Chem. Commun., 1994)
2. propylenexe2x86x92allyl acetate
3. phenol+allyl acetatexe2x86x922-allylphenol
4. 2-allylphenol +isophthalic acidxe2x86x92diester
5. diester+H2O2xe2x86x92diepoxide
6. diepoxide+succinic acidxe2x86x92epoxy resin
The following examples further illustrate novel epoxides of the present invention: